WO2012028658A2

WO2012028658A2 - Cosmetic aerosol spray

Info

Publication number: WO2012028658A2
Application number: PCT/EP2011/065043
Authority: WO
Inventors: Bernhard Banowski; Nadine Buse
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2010-09-01
Filing date: 2011-08-31
Publication date: 2012-03-08
Also published as: US9408787B2; EP2760421A2; WO2012028658A3; DE102010040121A1; US20130164238A1

Abstract

The invention relates to a cosmetic product comprising a water-in-oil emulsion containing: a) at least one cosmetic active ingredient, b) at least one water-in-oil emulsifier, c) at least one non-ionic polyalkylenglycol ether having a HLB-value > 7, d) at least one C₈-C₁₆ isoparaffin, also comprising at least one propellant and an aerosol dispensing device. The invention is characterised in that the emulsion has a high stability, a reduced susceptibility to corrosion, a good cosmetic effect and reduced formation of deposits during the application thereof.

Description

"Cosmetic Aerosol Spray"

The present application describes aerosol-sprayable cosmetic water-in-oil emulsions. Another object of this application is a method using appropriate emulsions.

An aerosol is a disperse system in which a solid or a liquid is very finely dispersed in a gas. The aerosol is usually only when using a suitable spray system by spraying solutions, emulsions or suspensions self-produced, including, for example, spray cans can be used, in which a liquefied compressed gas serves as a propellant gas. When the pressure valve is opened, the propellant preparation mixture escapes through a fine nozzle which evaporates the propellant and leaves the finely distributed spray material as an aerosol.

A technically important area for the application of cosmetic aerosol sprays is the field of deodorant cosmetic products. Common deodorant spray compositions are often present as anhydrous ethanolic solutions of the deodorizing agent. A disadvantage of these ethanolic solutions is a skin irritant effect in appropriately predisposed persons with sensitive skin. Even on skin mechanically irritated by shaving, the application of common ethanolic solutions leads to a very unpleasant burning sensation. A further disadvantage of ethanolic solutions is that the incorporation of water-containing or water-soluble active substances, in particular antiperspirant or deodorant active ingredients or hair growth inhibiting active ingredients which are not soluble in ethanol, is not or only to a very limited extent possible.

An alternative form of supply to the ethanolic solutions in the prior art, anhydrous suspensions of the powdered sweat reducing Wrkstoffes, usually an aluminum salt, in addition to the propellant in a liquid carrier, usually a relatively volatile oil such as cyclomethicones, discussed. Before spraying, the suspension must be shaken up. A disadvantage of these suspension aerosols is the risk that the valve or nozzle holes clog at higher salt concentrations. There have therefore been attempts to spray the antiperspirant salt in dissolved form. However, the formulation of aqueous antiperspirant salt solutions in propellant-containing metal cans causes great corrosion problems in the aerosol packaging, so that even with painted spray cans inevitably occur corrosion on the can.

As a further alternative form of supply, the prior art describes water-in-oil emulsions (W / O emulsions). For example, German Patent Application DE 10 2006 062 499 A1 (Henkel) discloses a W / O emulsion suitable as an aerosol spray. The emulsions disclosed in this application however contain cyclomethicones. Cyclomethicones have excellent performance properties, in particular with regard to emulsion stability, and for this reason are used in cosmetics, in particular in antiperspirants. If the amount of volatile cyclomethicones is too high, antiperspirants form after drying, ie only some time after the application, but on the skin white residues that adhere badly to the skin and are perceived by the consumer especially when they are transferred to dark garments as unpleasant.

It was an object of the present application to provide a stable water-in-oil emulsion having a low cyclomethicone and ethanol content which is suitable for use in an aerosol spray. The emulsion should also be characterized by a low tendency to corrosion when stored in a metallic spray can and by a good cosmetic, especially antiperspirant effect and low residue formation during application. In addition, the cosmetic active ingredient should be released particularly well from the W / O formulation.

It has been found that the stated object is achieved by water-in-oil emulsions based on a combination of a water-in-oil emulsifier, a specific polyalkylene glycol ether and a C ₈ -C ₆ isoparaffin.

A first subject of the present application is therefore a cosmetic product comprising

a water-in-oil emulsion containing

a) at least one cosmetic active substance,

b) at least one water-in-oil emulsifier,

c) at least one nonionic polyalkylene glycol ether having an HLB value> 7, d) at least one C ₈ -C ₆ isoparaffin,

at least one propellant,

an aerosol dispenser.

The water-in-oil emulsions according to the invention contain at least one cosmetic active substance. This cosmetic active substance is preferably selected from the group of antiperspirant active substances, deodorant active substances, antibacterial active substances, skin-care active ingredients, skin-tanning active ingredients, skin-lightening active ingredients, hair-care active substances and the sunscreen active ingredients. Also preferred are agents that reduce hair growth. The cosmetic active substance is preferably water-soluble.

In a first preferred embodiment, the water-in-oil emulsions according to the invention contain at least one antiperspirant active ingredient (antiperspirant active ingredient).

A preferred subject of the present application is a cosmetic product comprising

a water-in-oil emulsion containing

a) at least one antiperspirant active,

b) at least one water-in-oil emulsifier, c) at least one nonionic polyalkylene glycol ether having an HLB value> 7, d) at least one C ₈ -C ₆ isoparaffin,

- At least one propellant

Unless otherwise indicated, all amounts in this application are based on the weight of the inventive blowing agent-free water-in-oil emulsion.

Preferred antiperspirant active ingredients are selected from the water-soluble astringent inorganic and organic salts of aluminum and zinc or any desired mixtures of these salts. According to the invention, aluminosilicates and zeolites do not belong to the antiperspirant active ingredients. According to the invention, water solubility is understood to mean a solubility of at least 5% by weight at 20 ° C., that is to say amounts of at least 5 g of the antiperspirant active ingredient in 95 g of water 20 ° C are soluble.

Particularly preferred antiperspirant actives are selected from aluminum chlorohydrate, aluminum chlorohydrate, in particular having the general formula [Al ₂ (OH) ₅ CI ^■ 1 -6 H ₂ 0] _n, [AI preferably ₂ (OH) ₅ CI 2-3 ^■ H ₂ 0 ] _n , which may be in non-activated or in activated (= depolymerized) form, and aluminum chlorohydrate having the general formula [Al ₂ (OH) ₄ Cl ₂ ^■ 1 -6 H ₂ 0] _n , preferably [Al ₂ (OH ) ₄ CI ₂ ^■ 2-3 H ₂ 0] _n , which may be in unactivated or activated (= depolymerized) form.

Also preferred are aluminum sesquichlorohydrate, aluminum dichlorohydrate, or aluminum chlorohydrex polyethylene glycol (PEG), aluminum glycol complexes, e.g. B. aluminum-propylene glycol complexes Aluminiumsesquichlorohydrex-PG or Aluminiumsesquichlorohydrex-PEG, or aluminum-PEG dichlorohydrex, aluminum hydroxide, further selected from potassium aluminum sulphate (KAI (S0 ₄₎ ₂ ^■ 12 H ₂ 0, alum), Aluminiumundecylenoylcollagenaminosäure, sodium aluminum lactate + aluminum sulfate, sodium aluminum chlorhydroxylactate, aluminum bromohydrate, aluminum chloride, the complexes of zinc and sodium salts, the aluminum salts of lipoic amino acids, aluminum sulfate, aluminum lactate, aluminum chlorohydrate, sodium aluminum chlorohydroxactate, zinc chloride, zinc sulfocarbolate and zinc sulfate.

Antiperspirant active substances which are particularly preferred according to the invention are selected from what are known as "activated" aluminum salts, which are also referred to as "antiperspirant active substances" having increased activity (English: enhanced activity). Activated aluminum salts are typically produced by heat treating a relatively dilute solution of the salt (e.g., about 10% by weight of salt) to increase its HPLC peak 4-to-peak 3 area ratio. The activated salt can then be dried to a powder, in particular spray-dried. In addition to the spray drying z. B. also suitable for drum drying.

Activated aluminum salts typically have a HPLC peak 4-to-peak 3 area ratio of at least 0.4, preferably at least 0.7, more preferably at least 0.9, with at least 70% of the aluminum attributable to these peaks. Preferred amino acids for the stabilization of the antiperspirant salts are selected from glycine, alanine, leucine, isoleucine, β-alanine, valine, cysteine, serine, tryptophan, phenylalanine, methionine, β-amino-n-butanoic acid and γ-amino-n-butanoic acid and the salts thereof, each in the d-form, the I-form and the dl-form; Glycine is particularly preferred.

Preferred hydroxyalkanoic acids for the stabilization of the antiperspirant salts are selected from glycolic acid and lactic acid.

Other preferred antiperspirant actives are activated aluminum salts containing, by weight, 5-78% by weight (USP) of an activated antiperspirant aluminum salt, an amino acid or hydroxyalkanoic acid in such amount to be an (amino acid or hydroxyalkanoic acid) to Al weight ratio from 2: 1 to 1:20, and preferably from 1: 1 to 1:10, and a water-soluble strontium salt in such amount to have a Sr: Al weight ratio of 1: 1 to 1:28 and preferably 1: 2 to 1 : 25 to provide.

Particularly preferred solid antiperspirant activated salt compositions contain, based on their weight, 48-78% by weight (USP), preferably 66-75% by weight of an activated aluminum salt and 1-16% by weight, preferably 4-13% by weight. -% molecularly bound water, further enough so much water-soluble strontium salt that the Sr: Al weight ratio is 1: 1 - 1: 28, preferably 1: 2 - 1: 25, and so much amino acid that the amino acid to AI - weight ratio 2: 1 - 1: 20, preferably 1: 1 - 1: 10, is.

Further particularly preferred solid antiperspirant activated salt compositions contain, based on their weight, 48-78% by weight (USP), preferably 66-75% by weight of an activated aluminum salt and 1-16% by weight, preferably 4-13% by weight % molecularly bound water, further enough so much water-soluble strontium salt, that the Sr: Al weight ratio is 1: 1-1: 28, preferably 1: 2-1: 25, and so much glycine that the glycine is AI-weight ratio 2: 1-1: 20, preferably 1: 1-1: 10.

Further particularly preferred solid antiperspirant activated salt compositions contain, based on their weight, 48-78% by weight (USP), preferably 66-75% by weight of an activated aluminum salt and 1-16% by weight, preferably 4-13% by weight % molecularly bound water, further enough so much water-soluble strontium salt, that the Sr: Al weight ratio is 1: 1-1: 28, preferably 1: 2-1: 25, and so much hydroxyalkanoic acid that the hydroxyalkanoic acid is AI-weight ratio 2: 1-1: 20, preferably 1: 1-1: 10.

Further preferred activated aluminum salts are those of the general formula Al ₂ (OH) ₆ . _a Xa, wherein X is Cl, Br, I or N0 ₃ and "a" is a value of 0.3 to 5, preferably from 0.8 to 2.5 and particularly preferably 1 to 2, so that the molar ratio of Al X is 0.9: 1 to 2.1: 1. These salts generally associate some hydration water, typically 1 to 6 moles of water per mole of salt. Particularly preferred is aluminum chlorohydrate (ie, X is Cl in the aforementioned formula) and especially 5/6 basic aluminum chlorohydrate wherein "a" is 1 such that the molar ratio of aluminum to chlorine is 1.9: 1 to 2.1: 1 , Particularly preferred water-in-oil emulsions according to the invention comprise at least one antiperspirant active ingredient in a total amount of 5 to 40% by weight, preferably 10 to 30% by weight, more preferably 15 to 25% by weight and most preferably 20% to 23 wt .-%, each based on the total weight of the water-free active substance (USP) in the propellant-free water-in-oil emulsion.

In a particularly preferred embodiment, the water-in-oil emulsion contains an astringent aluminum salt, in particular aluminum chlorohydrate, more preferably aluminum chlorohydrate with an anhydrous active substance (USP) of 72-88 wt .-%, based on the raw material tel quel. In a further particularly preferred embodiment, the water-in-oil emulsion comprises a non-activated astringent aluminum salt, in particular aluminum chlorohydrate, particularly preferably aluminum chlorohydrate with an anhydrous active substance (USP) of 72-88 wt .-%, based on the raw material tel quel , Preferred non-activated aluminum chlorohydrates are, for example chlorohydrol ^® (Summit-Reheis), ACH 303 (Summit-Reheis) ^® Locron L (Clariant) or Aloxicoll L ^® (Giulini). A preferred activated aluminum chlorohydrate solution is z. B. ^Reach® 501 from Summit Reheis.

A preferred subject of the present application is a cosmetic product comprising

a water-in-oil emulsion containing

a) 5-40% by weight, based on the total weight of the water-free active substance (USP) in the propellant-free water-in-oil emulsion, an antiperspirant active substance from the group of antiperspirant aluminum salts,

b) at least one water-in-oil emulsifier,

at least one propellant,

an aerosol dispenser.

The water-in-oil emulsions according to the invention contain as second essential constituent at least one water-in-oil emulsifier. For the purposes of the present application, a water-in-oil emulsifier is considered to be a surface-active substance which has an HLB value in the range from 1, 5 to 6 under normal conditions. "Normal conditions" are a temperature of 20 ° for the purposes of the present application C and a pressure of 1013.25 hPa. Melting point data also refer to a pressure of 1013.25 hPa.

Water-in-oil emulsions in which the weight fraction of the water-in-oil emulsifier b), based on the total propellant-free water-in-oil emulsion, 0.2 to 4.0 wt .-%, preferably 0 , 3 - 3.0 wt .-% and in particular 0.4 to 2.0 wt .-%, are inventively preferred.

A particularly preferred group of water-in-oil emulsifiers according to the invention are the poly (C ₂ -C ₃ ) alkylene glycol-modified silicones whose previous INCI name was Dimethicone Copolyol, with the current INCI names PEG-x Dimethicone (with x = 2 - 20, preferably 3 to 17, more preferably 1 to 12), bis-PEG-y dimethicones (where y = 3 to 25, preferably 4 to 20), PEG / PPG a / b dimethicones (where a and b independently of one another represent numbers of 2-30, preferably 3-30 and particularly preferably 12-24, in particular 14-20, stand), bis-PEG / PPG-c / d dimethicones (where c and d independently of one another represent numbers of 10-25, preferably 14- 20 and more preferably 14-16) and bis-PEG / PPG-e / f PEG / PPG g / h dimethicones (wherein e, f, g and h independently represent numbers from 10-20, preferably 14-18 and 16 particularly preferred).

Particularly preferred water-in-oil emulsions according to the invention are characterized in that the water-in-oil emulsifier b) is selected from the group of alkoxylated silicone emulsifiers, preferably from the group of ethoxylated and propoxylated silicone emulsifiers, where Water-in-oil emulsifier b) with particular preference a substance from the group of PEG / PPG-n / m dimethicones with n + m> 1 1, in particular with n + m between 16 and 46, preferably with n + m between 26 and 46 is used. For clarification, it should be noted that these preferred water-in-oil emulsifiers b) from the group of PEG / PPG-n / m Dimethicone with n + m> 1 1, in particular with n + m between 16 and 46, preferably with n + m between 26 and 46, are alkylated only with methyl groups and - as the terms "dimethicone copolyol" and "PEG / PPG Dimethicone" already imply - no higher alkyl groups, eg. As ethyl, lauryl, cetyl, in the molecule.

Very particular preference is given to PEG / PPG-18/18 dimethicone. The particularly preferred water-in-oil emulsifier PEG / PPG-18/18 Dimethicone is commercially available not usually as a pure substance, but dispersed in a cosmetic oil. Preferred products according to the invention comprise a water-in-oil emulsion containing the water-in-oil emulsifier PEG / PPG-18/18 dimethicone as dispersion in dimethicone, which has a viscosity of 3 to 100 cSt, preferably 5 to 50 cSt, more preferably 10-20 cSt (each at 25 ° C). A particularly preferred commercial product is Dow Corning ES-5227 DM from Dow Corning. The weight fraction of the water-in-oil emulsifier b) is in total, based on the total propellant-free water-in-oil emulsion, preferably 0.2 to 4.0 wt .-%, preferably 0.3 to 3.0 wt .-% and in particular 0.4 to 2.0 wt .-%.

A preferred subject of the present application is a cosmetic product comprising

a water-in-oil emulsion containing

a) at least one antiperspirant active,

b) 0.2 to 4.0% by weight of water-in-oil emulsifier from the group of PEG / PPG-n / m dimethicones with n + m between 16 and 46, preferably with n + m between 26 and 46 , c) at least one nonionic polyalkylene glycol ether having an HLB value> 7, d) at least one C ₈ -C ₆ isoparaffin,

at least one propellant,

an aerosol dispenser. The water-in-oil emulsions according to the invention comprise as third essential constituent at least one nonionic polyalkylene glycol ether having an HLB value> 7. For the desired stability of emulsions according to the invention and the release of active substance of the antiperspirant active ingredient, an HLB value above 7 has proven to be advantageous , Preferred water-in-oil emulsions according to the invention are characterized in that the nonionic polyalkylene glycol ether c) has an HLB value> 9, preferably an HLB value> 12 and in particular an HLB value> 14. Particularly preferred nonionic polyalkylene glycol ethers c) have an HLB value of> 14 to 20, preferably from 15 to 18, particularly preferably from 15.5 to 17.

The HLB value is determined according to the invention according to Griffin according to the formula:

HLB = 20 * (M _h / M), where M _{h is} the molecular weight of the hydrophilic part of a molecule and M is the

Molar mass of the entire molecule. This results in a scale of 0 to 20.

Preferably, the polyalkylene glycol ether c) is selected from the group of the alkoxylated C ₈ -

C ₂₄ -alkanols with an average of 10 to 100 moles of alkylene oxide per mole, preferably from the group of ethoxylated C ₂ -C ₈ -alkanols with an average of 10 to 30 moles of ethylene oxide per mole, with nonionic polyalkylene glycol ethers c) with particular preference being an ethoxylated C ₄ -

C ₈ -alkanol is used with an average of 20 to 30 moles of ethylene oxide per mole. A particularly preferred polyalkylene glycol ether is an iso-ethyl alcohol ethoxylated with 20 moles of ethylene oxide

(Lsoceteth-20).

The weight fraction of the nonionic polyalkylene glycol ether c) is, based on the total propellant-free water-in-oil emulsion, preferably 0.1 to 4.0 wt .-%, preferably 0.2 to 2.0 wt .-% and in particular 0 , 5 to 1, 0 wt .-%.

A preferred subject of the present application is a cosmetic product comprising

a water-in-oil emulsion containing

a) at least one antiperspirant active,

b) at least one water-in-oil emulsifier,

c) 0.1 to 4.0% by weight of a nonionic polyalkylene glycol ether having an HLB value> 7 from the group of the alkoxylated C ₈ -C ₂₄ -alkanols with an average of 10 to 100 mol of alkylene oxide per mole,

d) at least one C ₈ -C ₆ isoparaffin,

at least one propellant,

an aerosol dispenser.

The water-in-oil emulsions according to the invention contain at least one C ₈ -C ₆ isoparaffin as the fourth essential constituent. The terms "isoparaffin" and "isoalkane" are used synonymously in the context of the present application. Preferred water-in-oil emulsions according to the invention are characterized in that the isoparaffin d) is selected from isooctane, isononane, isodecane, isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane, and Isohexadecan, and mixtures thereof, wherein C ₀ -C ₃ isoparaffin mixtures, especially those having a vapor pressure at 20 ° C of about 1-100 Pa, are preferred. Highly preferred are isoparaffins with a vapor pressure <40 Pa and> 8 Pa.

The proportion by weight of the isoparaffin c) is, based on the total propellant-free water-in-oil emulsion, a total of preferably 4.0 to 20 wt .-%, preferably 5.0 to 12 wt .-% and in particular 6.0 to 10 wt. -%.

A preferred subject of the present application is a cosmetic product comprising

a water-in-oil emulsion containing

a) at least one antiperspirant active,

b) at least one water-in-oil emulsifier,

c) at least one nonionic polyalkylene glycol ether having an HLB value> 7, d) 4.0 to 20 wt .-% of a C ₀ -C ₃ isoparaffin mixture,

at least one propellant,

an aerosol dispenser.

By the combination of

at least one water-in-oil emulsifier,

at least one nonionic polyalkylene glycol ether having an HLB value> 7 and

- At least one C ₈ -C ₆ isoparaffin

Stable emulsions with favorable release of the antiperspirant active substance and low residue formation with simultaneously low corrosion tendency could be produced.

Furthermore, it was possible to lower the cyclomethicone content of water-in-oil emulsions according to the invention without impairing the product properties. Preferred compositions according to the invention therefore contain, based on the total propellant-free water-in-oil emulsion, less than 5.0% by weight of cyclomethicones, preferably less than 3.0% by weight of cyclomethicones and more preferably less than 1.0% by weight .-% Cyclomethicone. Very particularly preferred compositions according to the invention are free of cyclomethicones. A preferred subject of the present application is a cosmetic product comprising

a water-in-oil emulsion containing

a) at least one antiperspirant active,

b) at least one water-in-oil emulsifier,

c) at least one nonionic polyalkylene glycol ether having an HLB value> 7, d) at least one C ₈ -C ₆ iso-paraffin,

at least one propellant,

an aerosol dispenser,

which, based on the weight of the total propellant-free water-in-oil emulsion, contains less than 5.0% by weight of cyclomethicone, preferably less than 3.0% by weight of cyclomethicone, more preferably contains less than 1, 0 wt .-% cyclomethicones and in particular no cyclomethicone.

As an optional constituent containing the water-in-oil emulsions according to the invention, preferably at least one ester of a C ₆ -C ₃₀ carboxylic acid. These include preferably 2-Ethylhexylpal- palmitate (z. B. Cegesoft ^® C 24), hexyldecyl stearate (z. B. Eutanol ^® G 16), hexyldecyl laurate, isodecyl neopentanoate, isononyl isononanoate, 2-ethylhexyl stearate, isopropyl myristate, isopropyl palmitate, iso propylstearat , Isopropyl isostearate, isopropyl oleate, isooctyl stearate, isononyl stearate, isocetyl stearate, isononyl isononanoate, isotridecyl isononanoate, cetearyl isononanot, 2-ethylhexyl laurate, 2-ethylhexyl isostearate, 2-ethylhexyl cocoate, 2-octyldodecyl palmitate, butyloctanoic acid 2-butyloctanoate, diisotridecyl acetate, n-butyl stearate, n-hexyl laurate , n-decyl oleate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, ethylene glycol dioleate and dipalmitate. The use of isopropyl esters of C ₂ -C ₈ -carboxylic acids, in particular the use of isopropyl myristate, has proved to be particularly advantageous for the emulsion stability and release of active ingredient.

The proportion by weight of the at least one C ₆ -C ₃₀ carboxylic acid ester, preferably C ₂ -C ₈ carboxylic acid ester, is in total, based on the total propellant-free water-in-oil emulsion, preferably 0.5-18% by weight. %, preferably 1, 0 - 16.0 wt .-%, in particular 2.0 - 14 wt .-% and most preferably 5 - 10 wt .-%.

A preferred subject of the present application is a cosmetic product comprising

a water-in-oil emulsion containing

a) at least one antiperspirant active,

b) at least one water-in-oil emulsifier,

e) 0.5 to 18% by weight of C ₂ -C ₈ -carboxylic acid ester,

at least one propellant,

an aerosol dispenser.

In a further preferred embodiment, the compositions according to the invention comprise at least one water-soluble polyol selected from the water-soluble polyhydric C ₂ -C 9 -alkanols having 2 to 6 hydroxyl groups and water-soluble polyethylene glycols having 3 to 20 ethylene oxide units and mixtures thereof. Particularly preferred water-in-oil emulsions according to the invention comprise at least one water-soluble polyhydric C ₂ -C ₉ -alkanol having 2 to 6 hydroxyl groups and / or at least one water-soluble polyethylene glycol having 3 to 20 ethylene oxide units.

Preferred water-in-oil emulsions according to the invention are characterized in that the water-in-oil emulsion furthermore comprises at least one water-soluble polyhydric C ₂ -C ₉ -alkanol having 2 to 6 hydroxyl groups and / or at least one water-soluble polyethylene glycol having 3 to 20 Ethylene oxide units selected from 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, glycerol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, Pentylene glycols like 1, 2-pentanediol and 1, 5-pentanediol, hexanediols such as 1, 6-hexanediol, hexanetriols such as 1, 2,6-hexanetriol, 1, 2-octanediol, 1, 8-octanediol, dipropylene glycol, tripropylene glycol, diglycerol, triglycerol rin, erythritol, sorbitol and mixtures of the aforementioned substances. These substances have a positive influence on the residue behavior, the emulsion stability and a storage-stable sprayability of the water-in-oil emulsions according to the invention. A particularly preferred water-soluble polyhydric C ₂ -C ₉ -alkanol with 2-6 hydroxyl groups is 1,2-propylene glycol.

The proportion by weight of the water-soluble polyhydric C ₂ -C ₉ -alkanol having 2 to 6 hydroxyl groups and / or the water-soluble polyethylene glycol having 3 to 20 ethylene oxide units is preferably, based on the total content of these substances in the propellant-free water-in-oil emulsion 0.5-35 wt .-%, preferably 1, 0 - 30 wt .-%, particularly preferably 2 - 25 wt .-%, more preferably 10 - 20 wt .-% or 12 - 15 wt .-%.

On the basis of the combination of emulsifier, polyalkylene glycol ether and paraffin according to the invention, it is possible to lower the ethanol content of water-in-oil emulsions according to the invention without impairing the product properties. Preferred water-in-oil emulsions according to the invention therefore contain, based on the total propellant-free water-in-oil emulsion, less than 4.0% by weight of ethanol, preferably less than 3.0% by weight of ethanol and more preferably less than 1.0% by weight of ethanol. Very particularly preferred compositions according to the invention are free of ethanol.

The water-in-oil emulsions of the compositions according to the invention contain water preferably in a total amount of 5 to 55 wt.%, Preferably 10 to 40 wt.%, Particularly preferably 15 to 30 wt.%, Most preferably 20 to 25 % By weight, in each case based on the weight of the total propellant-free water-in-oil emulsion.

The water-in-oil emulsions of the compositions of the invention preferably contain one or more preservatives. Preservatives preferred according to the invention are formaldehyde releasers (such as, for example, 1,3-dimethylol-4,4-dimethylhydantoin, INCI name DMDM hydantoin), iodopropynyl butylcarbamates such as 3-iodo-2-propynyl butylcarbamate, parabens (ie para-hydroxybenzoic acid alkyl esters, such as methyl , Ethyl, propyl and / or butylparaben), phenoxyethanol, ethanol, benzoic acid, dibromodicyanobutane (2-bromo-2-bromomethylglutarodinitrile), 2-bromo-2-nitro-propane-1,3-diol, imidazolidinylurea, 5 -Chloro-2-methyl-4-isothiazolin-3-one, 2-chloroacetamide, benzalkonium chloride, benzyl alcohol, salicylic acid and salicylates. Preservatives which are particularly preferred according to the invention are selected from parabens (methyl, ethyl, propyl and / or butylparaben) and / or phenoxyethanol.

The preservatives are in the water-in-oil emulsions according to the invention, based on the total propellant-free water-in-oil emulsion, preferably in a total amount of 0.01 to 3, preferably 0.1 to 1, 5 and particularly preferably 0 , 2 - 1, 0 wt .-%.

The composition of some preferred water-in-oil emulsions according to the invention can be found in the following tables (all data are in% by weight, based on the total weight of the water-in-oil emulsion without blowing agent): Antiperspirant active ingredient 5.0 to 40 10 to 40 15 to 40 20 to 40

Water-in-OI emulsifier 0.2 to 4.0 0.3 to 3.0 0.3 to 3.0 0.4 to 2.0 nonionic polyalkylene glycol ethers having 0.1 to 4.0 0.2 to 3 , 0 0.2 to 3.0 0.2 to 2.0 an HLB value> 7

C ₈ -C ₆ isoparaffin 4.0 to 20 4.0 to 20 5.0 to 12 6.0 to 10

in this as in the following tables: "-" equals "free of"

13 14 15 16

Antiperspirant aluminum salt 5.0 to 40 10 to 40 15 to 40 20 to 40

PEG / PPG-n / m dimethicones with n + m 0.2 to 4.0 0.3 to 3.0 0.3 to 3.0 0.4 to 2.0 between 26 and 46

nonionic polyalkylene glycol ether having 0.1 to 4.0 0.2 to 3.0 0.2 to 3.0 0.2 to 2.0 an HLB value> 7 from the group

alkoxylated C ₈ -C ₂₄ -alkanols with an average of 10 to 100 mol of alkylene oxide per

mol

C ₈ -C ₆ isoparaffin 4.0 to 20 4.0 to 20 5.0 to 12 6.0 to 10

Cyclomethicone <5.0 <3.0 <1.0

Ethanol <4.0 <3.0 <1, 0 _* 17 18 19 20

Antiperspirant aluminum salt 5.0 to 40 10 to 40 15 to 40 20 to 40

nonionic polyalkylene glycol ether having 0.1 to 4.0 0.2 to 3.0 0.2 to 3.0 0.2 to 2.0 an HLB value> 7

C ₀ -C ₃ isoalkane 4.0 to 20 4.0 to 20 5.0 to 12 6.0 to 10

Cyclomethicone <5.0 <3.0 <1.0

Ethanol <4.0 <3.0 <1, 0 _*

25 26 27 28

Antiperspirant aluminum salt 5.0 to 40 10 to 40 15 to 40 20 to 40

mol

C ₀ -C ₃ isoalkane 4.0 to 20 4.0 to 20 5.0 to 12 6.0 to 10

C ₂ -C ₈ carboxylic acid esters 0.5 to 18 1, 0 to 16 2.0 to 14 2.0 to 14

Cyclomethicone <5.0 <3.0 <1.0

Ethanol <4.0 <3.0 <1, 0 _* 29 30 31 32

Aluminum chlorohydrate 5.0 to 40 10 to 40 15 to 40 20 to 40

PEG / PPG-18/18 dimethicone 0.2 to 4.0 0.3 to 3.0 0.3 to 3.0 0.4 to 2.0 lsoceteth-20 0.1 to 4.0 0.2 to 3.0 0.2 to 3.0 0.2 to 2.0

C ₀ -C ₃ isoalkane 4.0 to 20 4.0 to 20 5.0 to 12 6.0 to 10

Isopropyl myristate 0.5 to 18 1, 0 to 16 2.0 to 14 2.0 to 14

Cyclomethicone <5.0 <3.0 <1.0

Ethanol <4.0 <3.0 <1, 0 _*

41 42 43 44

Antiperspirant aluminum salt 5.0 to 40 10 to 40 15 to 40 20 to 40

PEG / PPG-n / m Dimethicone with n + m 0.2 to 4.0 0.3 to 3.0 0.3 to 3.0 0.4 to 2.0 between 26 and 46 (W / O emulsifier )

C ₈ -C ₆ isoparaffin 4.0 to 20 4.0 to 20 5.0 to 12 6.0 to 10

Cyclomethicone <5.0 <3.0 <1, 0 _*

Ethanol <4.0 <3.0 <1, 0 _* C ₂ -C -alkanol with 2-6 hydroxyl groups 0.5-35 1.0-30 2-25 10-25 pen and / or water-soluble polyethylene glycol with 3-20 ethylene oxide units

in this as in the following tables: "-" equals "free of"

53 54 55 56

Antiperspirant aluminum salt 5.0 to 40 10 to 40 15 to 40 20 to 40

PEG / PPG-n / m Dimethicone with n + m 0.2 to 4.0 0.3 to 3.0 0.3 to 3.0 0.4 to 2.0 between 26 and 46 (W / O emulsifier ) nonionic polyalkylene glycol ether having 0.1 to 4.0 0.2 to 3.0 0.2 to 3.0 0.2 to 2.0 an HLB value> 7 from the group

alkoxylated C ₈ -C ₂₄ -alkanols with an average of 10-100 moles of alkylene oxide per

mol

C ₀ -C ₃ isoalkane 4.0 to 20 4.0 to 20 5.0 to 12 6.0 to 10

Cyclomethicone <5.0 <3.0 <1.0

Ethanol <4.0 <3.0 <1.0 _*

C ₂ -C -alkanol with 2-6 hydroxyl groups 0.5-35 1.0-30 2-25 10-25 pen and / or water-soluble polyethylene glycol with 3-20 ethylene oxide units

61 62 63 64

Aluminum chlorohydrate 5.0 to 40 10 to 40 15 to 40 20 to 40

PEG / PPG-18/18 dimethicone 0.2 to 4.0 0.3 to 3.0 0.3 to 3.0 0.4 to 2.0 (W / O emulsifier)

Isoceteth-20 0.1 to 4.0 0.2 to 3.0 0.2 to 3.0 0.2 to 2.0

C ₀ -C ₃ isoalkane 4.0 to 20 4.0 to 20 5.0 to 12 6.0 to 10

Isopropyl myristate 0.5 to 18 1.0 to 16 2.0 to 14 2.0 to 14

Cyclomethicone <5.0 <3.0 <1.0

Ethanol <4.0 <3.0 <1.0 _* 1, 2-propylene glycol 0.5 - 35 1, 0 - 30 2 - 25 10 - 25

In summary, cosmetic products comprising

a water-in-oil emulsion containing

a) 5-40% by weight of an antiperspirant active substance from the group of antiperspirant aluminum salts,

b) 0.2 to 4.0% by weight of water-in-oil emulsifier from the group of PEG / PPG-n / m dimethicones with n + m between 26 and 46,

d) 4.0 to 20% by weight of a C ₀ -C ₃ isoparaffin mixture,

e) 0.5 to 18% by weight of C ₁₂ -C ₁₈ carboxylic acid esters,

at least one propellant,

an aerosol dispenser,

Which

less than 5.0% by weight of cyclomethicones, preferably less than 3.0% by weight of cyclomethicones, more preferably less than 1.0% by weight of cyclomethicones and in particular no cyclomethicones, and

less than 4.0% by weight of ethanol, preferably less than 3.0% by weight of ethanol, more preferably less than 1.0% by weight of ethanol and in particular no ethanol,

wherein all wt .-% - in each case based on the weight of the propellant-free water-in-oil emulsion, most preferably.

Cosmetic products comprising

a water-in-oil emulsion containing

d) 4.0 to 20% by weight of a C ₀ -C ₃ isoparaffin mixture,

e) 0.5 to 18% by weight of C ₁₂ -C ₁₈ carboxylic acid esters,

at least one propellant,

an aerosol dispenser,

Which less than 5.0% by weight of cyclomethicones, preferably less than 3.0% by weight of cyclomethicones, more preferably less than 1.0% by weight of cyclomethicones and in particular no cyclomethicones, and

less than 4.0% by weight of ethanol, preferably less than 3.0% by weight of ethanol, more preferably less than 1.0% by weight of ethanol and in particular no ethanol, and

From 0.5 to 35% by weight, preferably from 1 to 30% by weight, more preferably from 2 to 25% by weight, and most preferably from 10 to 25% by weight, of at least one C _{2 to} C ₉ Alkanols having 2 to 6 hydroxyl groups and / or at least one water-soluble polyethylene glycol having 3 to 20 ethylene oxide units, which is preferably selected from 1, 2-propylene glycol,

wherein all wt .-% - in each case relate to the weight of the propellant-free water-in-oil emulsion, extremely preferred.

The water-in-oil emulsion of the invention is contained in an aerosol dispenser and the cosmetic product comprises at least one propellant.

Suitable propellants (propellant gases) according to the invention are propane, propene, n-butane, isobutane, isobutene, n-pentane, pentene, isopentane, isopentene, methane, ethane, dimethyl ether, nitrogen, air, oxygen, nitrous oxide, 1 , 1, 1, 3-tetrafluoroethane, heptafluoro-n-propane, perfluoroethane, monochlorodifluoromethane, 1, 1-difluoroethane, both individually and in combination. Also hydrophilic propellants, such. As carbon dioxide, can be used advantageously in the context of the present invention, when the proportion of hydrophilic gases is selected low and lipophilic propellant gas (eg., Propane / butane) is present in excess. Particularly preferred are propane, n-butane, isobutane and mixtures of these propellants.

Cosmetic products containing the propellant in an amount of 10 to 90% by weight, preferably 40 to 85% by weight and more preferably 50 to 80% by weight, based in each case on the total weight of the preparation consisting of the water in-oil emulsion and the propellant, are preferred according to the invention.

As pressure gas container come vessels made of metal (aluminum, tinplate, tin), protected or non-splitterndem plastic or glass, which is coated with plastic outside, in question, in their selection pressure and fracture resistance, corrosion resistance, easy fillability as well as aesthetic Aspects, handiness, printability etc. play a role. Special internal protective lacquers ensure corrosion resistance compared to the water-in-oil emulsion.

Despite the water phase in the aerosol container, the deodorant products according to the invention have a particularly high corrosion resistance, which represents a great advantage over the prior art. Furthermore, the water-in-oil emulsions used according to the invention have excellent skin tolerability, storage stability and effectiveness. It is particularly advantageous that the sprayed products on the skin by a pleasant, Characterize non-sticky skin sensation. The inventively balanced oil and water content creates a pleasant feeling of freshness with high skin compatibility after use. In a preferred embodiment of the invention, the valve has a coated with a paint or a polymeric plastic A valve disk and a similar flexible element with a return characteristic that the valve after completion of the operation in the closed position (= rest position of the valve) resets. Corresponding cosmetic products in which the aerosol dispenser comprises a valve having a poppet and / or a flexible element having a return characteristic coated with a lacquer or a polymeric plastic A are preferred according to the invention.

In a further preferred embodiment of the invention, the valve has a flexible element with a return characteristic and / or a valve disk of at least one plastic B, preferably an elastomeric plastic. Here too, cosmetic products according to the invention in which the valve has a flexible element with a return characteristic and / or a valve cone made from at least one plastic B are preferred, preferred plastics B being elastomeric plastics. Particularly preferred elastomeric plastics are selected from Buna, in particular Buna N, Buna 421, Buna 1602 and Buna KA 6712, neoprene, butyl and chlorobutyl.

In a further preferred embodiment of the invention, the flexible element with return characteristic can be formed as a spiral spring or helical compression spring. In a further preferred embodiment of the invention, the flexible element with return characteristic can be formed integrally with the valve cone and have flexible legs. This spring can be made of metal or plastic.

In a particularly preferred embodiment of the invention, valve cone and flexible element with a return characteristic are formed. Particularly preferred is the valve type Ariane M, available from the company Seaquist Perfect, in which the flexible element with restoring characteristic in the form of four elastic legs is formed integrally with the valve cone. All the valves used in the invention preferably have an internally painted valve disk, wherein paint and valve material are compatible with each other. If aluminum valves are used according to the invention, their valve disks can be internally z. B. be coated with Micoflex paint. If tinplate valves are used according to the invention, their valve disks can be internally z. B. be coated with PET (polyethylene terephthalate). The used containers, the z. B. tinplate or aluminum may be, aluminum containers are preferred according to the invention must also be painted or coated internally in view of the corrosivity of the present invention used in water-in-oil emulsions. An inventively preferred inner protective lacquer is an epoxy phenolic lacquer, as it u. a. Hoba 7407 P is available.

As stated at the outset, the agents according to the invention are suitable as cosmetic agents for the treatment of skin and hair. These agents are distinguished by an improved release of wrinkle and, as a consequence, by an improved cosmetic effect and a high level of cosmetic action Skin compatibility. Another object of the present application is therefore a process for the cosmetic treatment of skin and / or hair, characterized in that a water-in-oil emulsion containing

a) at least one cosmetic active substance,

b) at least one water-in-oil emulsifier,

in the form of an aerosol applied to the skin and / or the hair.

As stated at the outset, the agents according to the invention are suitable as deodorizing agents for the treatment of underarm wetness and body odor. These agents are characterized by an improved release of contaminants and, as a consequence, by an improved antiperspirant effect. Another object of the present application is therefore a process for the cosmetic treatment of body odor, characterized in that a water-in-oil emulsion containing

a) at least one antiperspirant active,

b) at least one water-in-oil emulsifier,

in the form of an aerosol is applied to the skin.

The following examples are intended to illustrate the subject matter of the invention without limiting it thereto.

The following four water-in-oil emulsions were prepared (% by weight) and checked for emulsion stability and corrosivity.

1 (V) 2 (V) 3 (V) 4 (E) 5 (E)

Aluminum chlorohydrate 33 33 33 33 33

Cyclomethicone 12 9,4

C ₀ -C ₃ isoalkane 9.4 8.9 8.9

PEG / PPG-18/18 dimethicones 1, 4 1, 4 1, 4 1, 4

Cetyl PEG / PPG-10/1 3.0

Dimethicone

Isoceteth-20 0.50 0.50

Dimethicone 0 4.2 4.2 4.2 4.2

Isopropyl myristate 9.0 9.0 9.0 9.0 9.0

1, 2 Propanediol 7.0 7.0 7.0 7.0 25

Phenoxyethanol 0.50 0.50 0.50 0.50 0.50 Perfume 2.5 2.5 2.5 2.5 2.5

Water ad 100 ad 100 ad 100 ad 100 ad 100

Stable emulsion no no no yes yes

Corrosivity no no

The noninventive composition 1 is based on a combination of cyclomethicone (oil phase) and cetyl PEG / PPG-10/1 dimethicone (water-in-oil emulsifier, used as Abil EM 90 from Evonik), according to the exemplary disclosure of water in-oil emulsions in the German patent application DE 10 2006 062 499 A1. Such a combination does not provide a stable emulsion.

Also, by replacing the water-in-oil emulsifier cetyl PEG / PPG-10/1 Dimethicone against the water-in-oil emulsifier PEG / PPG-18/18 Dimethicone (used as Dow Corning ES-5227 DM) (not Inventive example 2) no stable emulsion is obtained.

When exchanging cyclomethicones for C ₀ -C ₃ isoalkane can by using the water-in-oil emulsifier PEG / PPG-18/18 Dimethicone (used as Dow Corning ES-5227 DM) (not inventive example 3) also no stable Emulsion are obtained.

Only when C ₀ -C ₃ isoalkane (oil phase) is combined with an emulsifier combination of the water-in-oil emulsifier PEG / PPG-18/18 dimethicone (used as Dow Corning ES-5227 DM) and the oil-in-oil emulsifier. Water emulsifier isoceteth-20, the resulting emulsion is stable (Inventive Example 4). The resulting water-in-oil emulsion is non-corrosive when filled into an epoxy-phenolic-backed aluminum can at a weight ratio of propellant (butane / propane / isobutane mixture) to 80:20 emulsion.

* ex Dow Corning ES-5227 DM Emulsion No. 6 according to the invention showed a further improved residue behavior compared with emulsion No. 5 according to the invention, as the test results summarized below show:

Emulsion No. 5 left a narrow white circle (scale value 1, 1) when spraying a standardized amount onto blackboard after the drying time (scale value 1, 1), while emulsion No. 6 left almost no white residue (scale value 0.1).

In another test setup ("greasy / wet on black"), emulsion # 5 gave a residue scale value of 0.8, emulsion # 6 a residue scale value of 0.6.

Further formulation examples according to the invention

* ex Dow Corning ES-5227 DM

Claims

claims

1 . Cosmetic product comprising

a water-in-oil emulsion containing

a) at least one cosmetic active substance,

b) at least one water-in-oil emulsifier,

at least one propellant,

an aerosol dispenser.

2. Product according to claim 1, characterized in that the cosmetic active ingredient a) is selected from the group of antiperspirant active substances, in particular the antiperspirant aluminum salts.

3. Product according to one of the preceding claims, characterized in that the water-in-oil emulsifier b) is selected from the group of alkoxylated silicone emulsifiers, preferably from the group of ethoxylated and propoxylated silicone emulsifiers, wherein as water-in-oil Emulsifier b) is used with particular preference a substance from the group of PEG / PPG-n / m dimethicones with n + m> 1 1, in particular with n + m between 16 and 46, preferably with n + m between 26 and 46.

4. Product according to one of the preceding claims, characterized in that the weight fraction of the water-in-oil emulsifier b), based on the total propellant-free water-in-oil emulsion, 0.2 - 4.0 wt .-% , preferably 0.3 to 3.0 wt .-% and in particular 0.4 to 2.0 wt .-% is.

5. Product according to one of the preceding claims, characterized in that the nonionic polyalkylene glycol ether c) is selected from the group of alkoxylated C ₈ -C ₂₄ -alkanols with an average of 10 to 100 moles of alkylene oxide per mole, preferably from the group of ethoxylated C ₂ -C ₈ alkanols with an average of 10 to 30 moles of ethylene oxide per mole, with poly ethoxylated C ₄ -C ₈ alkanol having an average of 20 to 30 moles of ethylene oxide per mole being used as the polyalkylene glycol ether c).

6. Product according to one of the preceding claims, characterized in that the nonionic polyalkylene glycol ether c) has an HLB value> 9, preferably an HLB value> 12, in particular an HLB value> 14 and exceptionally preferably an HLB value of> 14 to 20, preferably from 15 to 18, particularly preferably from 15.5 to 17.

7. Product according to one of the preceding claims, characterized in that the weight fraction of the nonionic polyalkylene glycol ether c), based on the total propellant-free water-in-oil emulsion, 0.1 to 4.0 wt .-%, preferably 0.2 to 3.0 wt .-% and in particular 0.2 to 2.0 wt .-% is.

8. Product according to one of the preceding claims, characterized in that the isoparaffin d) is selected from isooctane, isononane, isodecane, isoundecane, isododecane, isotridecan, isotetradecane, isopentadecane, and isohexadecane, and mixtures thereof, wherein C ₀ -C ₃ isoparaffin mixtures, especially those having a vapor pressure at 20 ° C of about> 8 to <40 Pa are particularly preferred.

9. Product according to one of the preceding claims, characterized in that the weight fraction of the isoparaffin c), based on the total propellant-free water-in-oil emulsion, 4.0 to 20 wt .-%, preferably 5.0 to 12 wt .-% and in particular 6.0 to 10% by weight.

10. Product according to one of the preceding claims, characterized in that the water-in-oil emulsifier b) is selected from PEG / PPG-18/18 Dimethicone, preferably as a dispersion in Dimethicone, having a viscosity of 3 - 100 cSt , preferably 5 - 50 cSt, more preferably 10 - 20 cSt (each at 25 ° C), is present.

1 1. Product according to one of the preceding claims, characterized in that the water-in-oil emulsion at least one water-soluble polyol selected from the water-soluble polyhydric C ₂ - C ₉ alkanols having 2 - 6 hydroxyl groups and / or at least one water-soluble polyethylene glycol with 3rd - 20 ethylene oxide units, preferably selected from 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propanediol, glycerol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4 Butylene glycol, pentylene glycols such as 1, 2-pentanediol and 1, 5-pentanediol, hexanediols such as 1, 6-hexanediol, hexanetriols such as 1, 2,6-hexanetriol, 1, 2-octanediol, 1, 8-octanediol, dipropylene glycol, tripropylene glycol , Diglycerol, triglycerol, erythritol, sorbitol and mixtures of the aforementioned substances, and more preferably selected from 1,2-propylene glycol.

12. Product according to one of the preceding claims, characterized in that the weight fraction of the water-soluble polyhydric C ₂ - C ₉ alkanol having 2 - 6 hydroxyl groups and / or the water-soluble polyethylene glycol with 3 - 20 ethylene oxide units, based on the total content of these substances in the propellant-free water-in-oil emulsion, 0.5-35 wt .-%, preferably 1, 0 - 30 wt .-%, particularly preferably 2-25 wt .-%, more preferably 10 - 20 wt. % or 12-15% by weight.

13. Product according to one of the preceding claims, characterized in that the nonionic polyalkylene glycol ether c) is selected from Isoceteth-20.

14. A method for the cosmetic treatment of skin and / or hair, characterized in that a water-in-oil emulsion containing

a) at least one cosmetic active substance,

b) at least one water-in-oil emulsifier,

in the form of an aerosol applied to the skin and / or the hair.

15. A method for the cosmetic treatment of body odor, characterized in that a water-in-oil emulsion containing

a) at least one antiperspirant active,

b) at least one water-in-oil emulsifier,

in the form of an aerosol is applied to the skin.